DE69511387T2 - NEW GLYCINE DERIVATIVES, INTERMEDIATE PRODUCTS, AND THESE CLEANING COMPOSITIONS CONTAINING THEM - Google Patents

Description

The invention relates to new glycine derivatives with low skin irritation and good foaming ability, processes for their preparation and cleaning compositions containing such glycine derivatives.

Furthermore, the invention relates to other glycine derivatives which are useful as intermediates for the synthesis of the above-mentioned glycine derivatives and are themselves useful as cleaners, processes for their preparation and cleaning compositions containing such glycine derivatives.

Furthermore, the invention relates to a method for washing skin or hair using such a cleaning composition, in other words to a use of the cleaning composition.

The cleaning compositions of the invention exhibit excellent foaming, are non-slimy and non-sticky, exhibit excellent foam breaking up during rinsing, exhibit reduced skin irritation and are excellent in terms of storage stability.

STATE OF THE ART:

In recent years it has become necessary to investigate the effects of surfactants used as cleaners on the environment. In other words, it has become necessary for the surfactants to be excellent in biodegradability and safety and to show reduced irritation to the skin and eyes. Various surfactants such as acylated amino acids, imidazole surfactants, alkyl phosphate salts, betaine surfactants and saccharide surfactants have been developed and used as surfactants that meet these requirements.

Although these surfactants are excellent in environmental protection and safety, their foaming ability and detergency are generally not satisfactory. Therefore, the surfactants generally used for, for example, a shampoo, a body cleanser or a dishwashing detergent are still anionic surfactants such as higher fatty acid salts (soaps), alkyl sulfates (AS), polyoxyethylene alkyl ether sulfates (ES) and alkyl sulfonates, and the above-mentioned surfactants are used only as auxiliary agents.

For example, when soap is used for skin cleansing, soap scum (calcium salt of higher fatty acid) is formed and adheres to the skin during rinsing, so that the smoothness of the skin surface is considerably reduced, resulting in squeaking and stiffness. When an alkyl sulfate or an alkyl sulfonate is used for skin cleansing, it is poor in foam breaking and causes a problem in terms of comfort of use due to sliminess and stickiness, although it does not cause squeaking and stiffness. Therefore, various auxiliary agents such as oils, e.g., a higher alcohol, and auxiliary cleaners are included in cleansing compositions such as shampoos, body cleansers and dishwashing detergents. However, use of such adjuvants results in deterioration of detergency, foaming ability, ease of use and the like, so that the types and amounts of adjuvants that can be used are subject to various restrictions. It has therefore been difficult to obtain detergent compositions having satisfactory performances.

Under these circumstances, cleaning compositions each containing an acylaminodibasic acid type anionic surfactant have been proposed (see JP-A Nos. 54-30207, 5-117139 and 6-80987). Although these cleaning compositions are improved in detergency, foaming ability and ease of use compared with those of the prior art, they have a disadvantage that storage stability is poor, particularly at low temperatures, since the acylaminodibasic acid type anionic surfactants are derivatives of an iminodiacetic acid:

DE-A-37 17 961 discloses a process for preparing compounds of general formula (I)

where R₁ can be a C₁₋₂₂ alkyl or alkoxyalkyl group, R₂ can be e.g. a C₁₋₁₈ alkyl group, R₃ is H or CH₃, · is H, an (alkaline earth) metal, ammonium, alkylammonium or alkanolammonium, and A can be e.g. = CO-:

These compounds can be used as emulsifiers or as surfactants in cleaning compositions or for the preparation of water repellents for leather.

JP-A-05125027 describes alkyl or alkenyl succinic acid derivatives useful as surfactants with low skin irritability and excellent detergency against stains on fibers.

Consequently, there has been a great demand in the art for the development of surfactants which are excellent in environmental protection and safety, which exhibit good foaming ability and detergency, which are excellent in convenience of use, and which can be used for various purposes. There is also a demand for such surfactants which exhibit excellent storage stability when used as a component of a cleaning composition.

Accordingly, it is an aim of the invention to provide new surfactants.

It is a further object of the invention to provide surfactants having excellent environmental protection properties, safety, foaming ability, detergency and convenience of use and having applicability for various purposes, which are useful as cleaners for hair, body and tableware.

It is a further aim of the invention to provide new processes for producing such surfactants.

It is a further aim of the invention to provide new intermediates for the production of such surfactants.

It is a further aim of the invention to provide new processes for the preparation of such intermediates.

It is a further object of the invention to provide new compositions containing such surfactants.

It is a further object of the invention to provide novel compositions containing such surfactants which exhibit excellent foaming and foam stability, are slime-free and non-sticky, exhibit excellent foam breaking upon rinsing, have reduced irritation and are excellent in storage stability at low temperatures.

It is a further object of the invention to provide a new method of washing skin or hair with such a composition.

It is a further object of the invention to provide a new use of such a composition for washing skin or hair.

These and other objects, which will become apparent from the following detailed description, have been achieved by the inventors' discovery that amide surfactants, each having two hydrophilic groups derived from glycine, are excellent in environmental protection and safety, a have good foaming ability and good detergency, are excellent in terms of user comfort and can be used for various purposes.

Furthermore, these and other objects have been achieved by the inventors' discovery that the cleaning compositions comprising an amide surfactant having two hydrophilic groups derived from glycine and a specific sugar surfactant, a specific ether type acetic acid type or a specific fatty acid amide derivative are excellent in foaming and foam stability, are non-slimy and non-sticky, and exhibit excellent foam breaking during rinsing, have reduced irritation and are excellent in storage stability at low temperatures. Thus, the invention provides glycine derivatives represented by the following formulas (1) to (4):

wherein R is a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 1 to 13 carbon atoms, and M₁ and M₂ are the same or different from each other and each independently represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a trialkanolammonium group having a total of 3 to 22 carbon atoms, or a protonated basic amino acid.

In formula (3), M₁ and M₂ do not represent a hydrogen atom or an alkali metal atom, and in formula (4), M₁ does not represent a hydrogen atom. Such compounds are known from Chemical Abstract No. 119: 141674 and US-A-4,650,613, respectively.

Thus, the invention provides:

(i) a process for producing the glycine derivative represented by the above formula (1), which comprises hydrolyzing the cyano group of the glycine derivative represented by the above formula (2), and optionally then subjecting it to salt exchange;

(ii) a process for producing the glycine derivative represented by the above formula (1), which comprises reacting the glycine derivative represented by the above formula (3) glycine derivative with an acid chloride represented by the formula (6) RCOCl (wherein R is as defined above) and optionally subsequent salt exchange;

(iii) a process for producing the glycine derivative represented by the above formula (1), which comprises a step of reacting glycine or a salt thereof represented by the formula (5):

(wherein M₁ is as defined above) with acrylonitrile;

(iv) a process for producing the glycine derivative represented by the above formula (1), which comprises a step of reacting glycine or a salt thereof represented by the formula (5):

(wherein M₁ is as defined above) with acrylonitrile to obtain a glycine derivative represented by the above formula (4), and a step of reacting the glycine derivative represented by the above formula (4) with an acid chloride represented by the formula (6): RCOCl (wherein R is as defined above), and optionally subsequently subjecting it to salt exchange;

(v) a process for producing the glycine derivative represented by the above formula (1), which comprises a step of reacting glycine or a salt thereof represented by the formula (5):

(wherein M₁ is as defined above) with acrylonitrile, to obtain a glycine derivative represented by the above formula (4), and a step of hydrolyzing the cyano group of the glycine derivative represented by the above formula (4), and optionally subsequently subjecting it to salt exchange;

(vi) a process for producing the glycine derivative represented by the above formula (1), which comprises a step of reacting glycine or a salt thereof represented by the formula (5)

(wherein M₁ is as defined above) with acrylonitrile to obtain a glycine derivative represented by the above formula (4), a step of reacting the glycine derivative represented by the above formula (4) with an acid chloride represented by the formula (6): RCOCl (wherein R is as defined above), and optionally thereafter salt exchange to obtain the glycine derivative represented by the above formula (2), and a step of hydrolyzing the cyano group of the glycine derivative represented by the above formula (2), and optionally thereafter salt exchange;

(vii) a process for producing the glycine derivative represented by the above formula (1), which comprises a step of reacting glycine or a salt thereof represented by the formula (5):

(wherein M₁ is as defined above) with acrylonitrile to obtain the glycine derivative represented by the above formula (4), a step of hydrolyzing the glycine derivative represented by the above formula (4) and optionally then subjecting it to salt exchange to obtain the glycine derivative represented by the above formula (3), and a step of reacting the glycine derivative represented by the above formula (3) with an acid chloride represented by the formula (6): RCOCl (wherein R is as defined above) and optionally subjecting it to salt exchange;

(viii) a process for producing the glycine derivative represented by the above formula (1), which comprises using the glycine derivative represented by the above formula (2); and

(ix) a process for producing the glycine derivative represented by the above formula (1), which comprises using the glycine derivative represented by the above formula (4).

The invention further provides:

(i) a process for producing the glycine derivative represented by the above formula (2), which comprises reacting the glycine derivative represented by the above formula (4) with an acid chloride represented by the formula (6): RCOCl (wherein R is as defined above) and optionally then subjecting it to salt exchange;

(ii) a process for producing the glycine derivative represented by the above formula (2), which a step of reacting glycine or a salt thereof represented by the formula (5)

(wherein M₁ is as defined above) with acrylonitrile;

(iii) a process for producing the glycine derivative represented by the above formula (2), which comprises a step of reacting glycine or a salt thereof represented by the formula (5):

(wherein M₁ is as defined above) with acrylonitrile to obtain the glycine derivative represented by the above formula (4), and a step of reacting the glycine derivative represented by the above formula (4) with an acid chloride represented by the formula (6): RCOCl (wherein R is as defined above), and optionally subsequently subjecting it to salt exchange; and

(iv) a process for producing the glycine derivative represented by the above formula (2), which comprises using the glycine derivative represented by the above formula (4).

The invention further provides:

(i) a process for producing the glycine derivative represented by the above formula (3), which comprises hydrolyzing the cyano group of the glycine derivative represented by the above formula (4) and optionally then subjecting it to salt exchange;

(ii) a process for producing the glycine derivative represented by the above formula (3), which comprises a step of reacting glycine or a salt thereof represented by the formula (5):

(wherein M₁ is as defined above) with acrylonitrile;

(iii) a process for producing the glycine derivative represented by the above formula (3), which comprises a step of reacting glycine or a salt thereof represented by the formula (5):

(wherein M₁ is as defined above) with acrylonitrile to obtain the glycine derivative represented by the above formula (4), and a step of hydrolyzing the cyano group of the glycine derivative represented by the above formula (4), and optionally then subjecting the glycine derivative to salt exchange; and

(iv) a process for producing the glycine derivative represented by the above formula (3), which comprises using the glycine derivative represented by the above formula (4).

In addition, the invention provides a process for producing a glycine derivative represented by the above formula (4), which comprises reacting glycine or a salt thereof represented by the formula (5):

(where M1 is as defined above) with acrylonitrile .

The invention also provides:

(i) a cleaning composition comprising the glycine derivative represented by the above formula (1);

(ii) a cleaning composition comprising the glycine derivative represented by the above formula (1) and a sugar surfactant represented by the formula (7): R¹-(OR²)m-Gn (wherein R¹ is a straight-chain or branched alkyl group having 8 to 18 carbon atoms, a straight-chain or branched alkenyl group having 8 to 18 carbon atoms, or a substituted phenyl group having a straight-chain or branched alkyl group having 8 to 18 carbon atoms, R² is an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar having 5 to 6 carbon atoms, m is a number from 0 to 10, and n is a number from 1 to 10);

(iii) a cleaning composition comprising the glycine derivative represented by the above formula (1) and an ether type acetic acid surfactant represented by the formula (8): R³-Z-(CH₂CH₂O)l-CH₂CO₂X (wherein R³ is a straight-chain or branched alkyl group having 5 to 21 carbon atoms or a straight-chain or branched alkenyl group having 5 to 21 carbon atoms, Z is a group represented by the formula -O- or a group represented by the formula -CONH-, X is a hydrogen atom, an alkali metal atom, 1/2(alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a trialkanolammonium group having a total of 3 to 22 carbon atoms or a protonated basic amino acid, and 2 is a number from 2 to 15);

(iv) a cleaning composition comprising the glycine derivative represented by the above formula (1) and a fatty acid amide derivative represented by the formula (9)

(wherein R⁴ is a straight-chain or branched alkyl group having 7 to 21 carbon atoms, and R⁵ and R⁴ are the same or different from each other and each independently is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a group represented by the formula -(C₂H₄O)kH (wherein k is a number from 2 to 4); and

(v) a cleaning composition comprising the glycine derivative represented by the above formula (2). Of the cleaning compositions of the present invention, those having a pH of 4 to 6.5 are preferred.

Furthermore, the invention provides a method for washing skin or hair, which comprises bringing the skin or hair into contact with the above-described cleaning composition according to the invention, and a use of the above-described Cleansing composition for washing skin or hair:

A more complete appreciation of the invention and many of the attendant advantages will be readily obtained when the same becomes better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings.

Fig. 1 is the 1H NMR spectrum of sodium N-cyanoethylglycinate obtained in Example 1;

Fig. 2 is the 1H NMR spectrum of N-cyanoethyl-N-dodecanoylglycine obtained in Example 2;

Fig. 3 is the 1H NMR spectrum of N-carboxyethyl-N-dodecanoylglycine obtained in Example 6;

Fig. 4 is the 1H NMR spectrum of disodium N-carboxyethylglycinate obtained in Example 7.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS:

In the above-mentioned formulas (1) and (2), R is a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms. Specific examples thereof include n-undecyl group, n-dodecyl group, n-tridecyl group and hydroxyundecyl group. Of these, surfactants in which R is a straight-chain or branched alkyl group having 11 to 13 carbon atoms and other surfactants in which R is a straight-chain or branched alkenyl group having 11 to 13 carbon atoms are preferred in view of foaming ability, and those in which R represents a straight-chain alkyl group having 11 to 13 carbon atoms are particularly preferred. When the surfactant represented by the above-mentioned formula (1) or (2) is a mixture of compounds differing from each other only in the carbon number of the acyl group, those having an average carbon number calculated from the carbon numbers of R's of the above-described compounds of 11 to 13 are included in the range of the surfactants of the present invention.

In formulas (1), (2), (3) and (4), M₁ and M₂ are the same or different from each other and each independently represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having 2 to 22 carbon atoms in total, a trialkanolammonium group having 2 to 22 carbon atoms in total, or a protonated basic amino acid. The protonated basic amino acid group includes protonated basic amino acids and inorganic salts thereof.

Specific examples of M₁ and M₂ include a hydrogen atom, a sodium atom, a potassium atom, 1/2(magnesium atom), 1/2(calcium atom), an ammonium group, a monoethanolammonium group, a diethanolammonium group, a triethanolammonium group, a protonated glutamine, a protonated arginine, a protonated histidine and a protonated lysine. Of these, a hydrogen atom, a sodium atom, a potassium atom, 1/2(magnesium atom), an ammonium group, a monoethanolammonium group, a diethanolammonium group and a triethanolammonium group are preferred. A hydrogen atom, a sodium atom, a potassium atom and an ammonium group are particularly preferred.

The following compounds and salts thereof may be mentioned as specific examples of the glycine derivatives represented by the above formula (1) of the present invention:

The glycine derivative of the present invention represented by the above general formula (1) (hereinafter referred to simply as "glycine derivative (1)") can be synthesized by the following synthesis route.

where R, M₁ and M₂ are as defined above.

That is, the glycine derivative (1) of the present invention can be easily prepared by the following steps A, C and D or the steps A, B and E carried out in this order.

Level A:

This step involves reacting glycine or a salt thereof represented by the formula (5):

wherein M₁ is as defined above (hereinafter referred to simply as "glycine or salt thereof (5)") with acrylonitrile to obtain a glycine derivative represented by the formula (4):

where M1 is as defined above (hereinafter referred to simply as "glycine derivative (4)").

Level B:

This step involves hydrolyzing the cyano group of the glycine derivative (4), optionally followed by a salt exchange to obtain a glycine derivative represented by the formula (3):

wherein M₁ and M₂ are each as defined above (hereinafter referred to simply as "glycine derivative (3)").

Level C:

This step involves reacting the glycine derivative (4) with an acid chloride represented by the formula (6): RCOCl (6)

where R is as defined above (hereinafter referred to simply as "acid chloride (6)"), optionally followed by salt exchange to obtain a glycine derivative represented by formula (2):

where R and M₁ are as defined above (hereinafter referred to simply as "glycine derivative (2)").

It seems that the preparation of the compound represented by the formula

(wherein R and M₁ are each as defined above), which is similar to the glycine derivative (2) in chemical structure, is difficult to produce on an industrial scale.

Level D:

This step involves hydrolyzing the cyano group of the glycine derivative (2), optionally followed by a salt exchange to obtain the glycine derivative (1).

Level E:

This step involves reacting the glycine derivative (3) with an acid chloride (6), optionally followed by a salt exchange to obtain the glycine derivative (1).

Each of the above stages is described in detail below.

Level A:

In this step, glycine or a salt thereof (5) is reacted with acrylonitrile to obtain the glycine derivative (4).

The glycine or the salt thereof and acrylonitrile as starting materials may be those prepared by known methods or those commercially available. If necessary, the starting materials may be purified by recrystallization, distillation or otherwise before use.

Specific examples of glycine or the salt thereof (5) include glycine, sodium glycinate, potassium glycinate, lithium glycinate, magnesium glycinate, calcium glycinate and ammonium glycinate. Of these, sodium glycinate, potassium glycinate and ammonium glycinate are particularly preferred.

In this step, the glycine derivative (4) can be obtained by reacting one equivalent of glycine or the salt thereof (5) with 0.5 to 10 equivalents, preferably 0.75 to 5 equivalents, of acrylonitrile in water at a suitable temperature between 10 and 100°C, preferably between 30 and 70°C, for 0.5 to 100 hours, preferably 1 to 3 hours, optionally followed by counter ion exchange using, for example, an electrodialyzer. If the reaction time is more than 100 hours, side reactions such as hydrolysis of the cyano group disadvantageously occur. In this reaction, it is preferred that acrylonitrile is gradually added to the aqueous solution of glycine or the salt thereof (5) in order to obtain an improved yield due to the considerable reduction of side reactions such as polymerization of acrylonitrile.

The glycine derivative (4) obtained in this step can be used as it is in the following step. However, if desired, it can be recrystallized using a solvent such as water, methanol and ethanol to thereby obtain a highly purified product.

The glycine derivative (4) thus obtained is also a new substance.

The following compounds can be mentioned as specific examples of the glycine derivative (4):

Level B:

In this step, the cyano group of the glycine derivative (4) obtained in step A is hydrolyzed preferably in the presence of a basic substance to thereby obtain a glycine derivative (3).

Examples of basic substances to be used in this step include alkali metal hydroxides and Alkaline earth metal hydroxides. Specific examples include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide.

In this step, the glycine derivative (3) can be obtained by reacting the glycine derivative (4) in the presence of 0.1 to 30 equivalents, preferably 0.5 to 15 equivalents, with respect to 1 equivalent of the glycine derivative (4), of the basic substance in the presence of water and, if necessary, a polar solvent such as methanol, ethanol, isopropanol, acetone, 1,3-propanediol and propylene glycol, at a suitable temperature between 50 and 100°C, preferably between 70 and 100°C, for 0.5 to 100 hours, optionally followed by counter ion exchange using an electrodialyzer.

The glycine derivative (3) obtained in this step can be used as it is in the following step. However, if desired, it can be recrystallized using a solvent such as water, methanol and ethanol to thereby obtain a highly purified product. The glycine derivative (3) thus obtained is also a novel substance. The following compounds can be mentioned as specific examples of the glycine derivative (3):

Level C:

In this step, the glycine derivative (4) obtained in step A is reacted with an acid chloride (6), preferably in the presence of an alkaline substance, to thereby obtain a glycine derivative (2).

The acid chloride (6) as one of the starting materials may be one prepared by known methods or one commercially available. If necessary, the starting material may be purified by distillation or otherwise before use. Specific examples of the acid chlorides (6) include fatty acid chlorides of simple composition such as Dodecanoyl chloride and tetradecanoyl chloride, and fatty acid chlorides of mixed composition, such as cocoyl chloride.

In this step, the glycine derivative (2) can be obtained by reacting one equivalent of the glycine derivative (4) with generally 0.8 to 5.0 equivalents, preferably 0.9 to 1.3 equivalents, of the acid chloride (6) in the presence of water and, if necessary, a polar solvent such as methanol, ethanol, isopropanol, acetone, 1,3-propanediol and propylene glycol, at a suitable temperature between 0 and 100°C, preferably between 10 and 50°C, for 0.5 to 100 hours, optionally followed by counter ion exchange using an electrodialyzer.

When the amount of the acid chloride (6) used is less than the above range, the glycine derivative (4) disadvantageously remains unreacted in a large amount in the reaction mixture. On the other hand, when it is over this range, a large amount of fatty acids are produced as by-products from unreacted acid chloride (6).

In this step, it is preferable that an alkaline substance is added to the reaction system so that the pH of the system remains on the alkaline side, preferably the pH remains in the range of 9.0 to 11.0, in order to ensure the reactivity by suppressing the decomposition of the acid chloride (6). If the pH of the reaction system is below the above range, the hydrochloric acid produced as a by-product according to the progress of the reaction reacts with unreacted glycine derivative (4) to form a salt, so that the reaction does not proceed satisfactorily. On the other hand, if the If the pH value is above this range, the decomposition of the acid chloride (6) is promoted, producing fatty acids as by-products in large quantities.

Specific examples of the alkaline substances to be used include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and sodium carbonate, and organic bases such as triethylamine, pyridine and 4-dimethylaminopyridine. Of these, sodium hydroxide and potassium hydroxide are particularly practical. These alkaline substances are used in such amounts that the pH of the system can be maintained in the above range.

The glycine derivative (2) obtained in this step can be used as it is in the subsequent step. However, if desired, it can be recrystallized using a solvent such as water, methanol and ethanol. Alternatively, the glycine derivative (2) can be purified by treating it with a strong acid such as hydrochloric acid and sulfuric acid to thereby obtain a glycine derivative (2) in acid form, and then recrystallizing this acidic derivative from a solvent such as acetone, hexane, petroleum ether, methanol, ethanol and butanol, and thereafter neutralizing it with an appropriate neutralizer to thereby obtain a glycine derivative (2). Thus, highly purified glycine derivative (2) can be obtained.

The glycine derivative (2) thus obtained is also a new substance.

The following compounds or salts thereof may be mentioned as specific examples of the glycine derivatives (2):

Level D:

In this step, the cyano group of the glycine derivative (2) obtained in step C is hydrolyzed preferably in the presence of a basic substance to thereby obtain a glycine derivative (1).

Examples of basic substances to be used in this step include alkali metal hydroxides and alkaline earth metal hydroxides. Specific examples of these include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide.

In this step, the glycine derivative (1) can be obtained by reacting the glycine derivative (2) in the presence of 0.1 to 30 equivalents, preferably 0.5 to 15 equivalents, with respect to 1 equivalent of the glycine derivative (2) of the basic substance in the presence of water and, if necessary, a polar solvent such as methanol, ethanol, isopropanol, acetone, 1,3-propanediol and propylene glycol at a suitable temperature between 50 and 100°C, preferably between 70 and 100°C for 0.5 to 100 hours, optionally followed by counter ion exchange using an electrodialyzer.

The glycine derivative (1) obtained in this step can be used as it is as a component for, for example, a cleaning composition. However, if desired, it can be recrystallized using a solvent such as water, methanol and ethanol. Alternatively, the glycine derivative (1) can be purified by treating it with a strong acid such as hydrochloric acid and sulfuric acid to thereby obtain a glycine derivative (1) in acid form, then recrystallizing this acidic derivative from a solvent such as acetone, hexane, petroleum ether, methanol, ethanol and butanol, and then neutralizing it with a suitable neutralizer to thereby obtain a glycine derivative (1). Thus, highly purified glycine derivative (1) can be obtained.

Level E:

In this step, the glycine derivative (3) obtained in step B is reacted with an acid chloride (6) preferably in the presence of an alkaline substance to thereby obtain a glycine derivative (1).

The acid chloride (6) as one of the starting materials is the same as that used in the above step C. In this step, the glycine derivative (1) can be prepared by reacting 1 equivalent of the glycine derivative (3) with generally 0.8 to 5.0 equivalents, preferably 0.9 to 1.3 equivalents of the acid chloride (6) in the presence of water and, if necessary, a polar solvent such as methanol, ethanol, isopropanol, Acetone, 1,3-propanediol and propylene glycol, at a suitable temperature between 0 and 100°C, preferably between 10 and 50°C, for 0.5 to 100 hours, optionally followed by counter ion exchange using an electrodialyzer.

When the amount of acid chloride (6) used is less than the above range, the glycine derivative (3) remains unreacted in a large amount in the reaction mixture, disadvantageously. On the other hand, when it is over this range, a large amount of fatty acid is produced as a by-product from unreacted acid chloride (6).

In this step, it is preferable that an alkaline substance is added to the reaction system so that the pH of the system remains on the alkaline side, preferably that the pH remains in the range of 9.0 to 11.0 to ensure the reactivity by suppressing the decomposition of the acid chloride (6). If the pH of the reaction system is below the above range, the hydrochloric acid produced as a by-product according to the reaction reacts with unreacted glycine derivative (3) to form a salt, so that the reaction does not proceed satisfactorily. On the other hand, if the pH is above this range, the decomposition of the acid chloride (6) is promoted, whereby fatty acids are produced in large amounts as by-products.

Specific examples of the alkaline substances to be used in this step include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and sodium carbonate, and organic bases such as triethylamine, pyridine and 4-dimethylaminopyridine. Sodium hydroxide and potassium hydroxide are particularly useful in these cases. These alkaline substances are used in such quantities that the pH of the system can be maintained within the above range.

The glycine derivative (1) obtained in this step can be used as it is as a component for, for example, a cleaning composition. However, if desired, it can be subjected to the same post-treatment as in step D to thereby obtain a product of increased purity.

The glycine derivatives (1) and (2) of the present invention are novel surfactants which are excellent not only in safety, but also in foaming ability, detergency, convenience in use and general usability and are suitable for use as a component of a cleaning composition for, e.g., hair, body or tableware.

The cleaning composition of the present invention contains the glycine derivative (1) or (2) as an essential component. The cleaning composition of the present invention may contain one of the glycine derivatives (1) or two or more thereof. The cleaning composition of the present invention may contain one of the glycine derivatives (2) or two or more thereof. The amount of the glycine derivative (1) or (2) contained is preferably 0.1 to 99% by weight, more preferably 0.1 to 70% by weight, based on the total weight of the composition. Typically, the composition will also contain water.

The cleaning composition containing the glycine derivative (1) of the present invention may further contain a sugar surfactant represented by the formula (7):

R¹-(OR²)m-Gn (wherein R¹ represents a straight-chain or branched alkyl group having 8 to 18 carbon atoms, a straight-chain or branched alkenyl group having 8 to 18 carbon atoms, or a substituted phenyl group having a straight-chain or branched alkyl group having 8 to 18 carbon atoms, R² represents an alkylene group having 2 to 4 carbon atoms, G is a residue derived from a reducing sugar having 5 to 6 carbon atoms, m is a number from 0 to 10, and n is a number from 1 to 10); an ether type acetic acid surfactant represented by the following formula (8): R³-Z-(CH₂CH₂O)l-CH₂CO₂X (wherein R³ represents a straight-chain or branched alkyl group having 5 to 21 carbon atoms or a straight-chain or branched alkenyl group having 5 to 21 carbon atoms, Z represents a group represented by the formula -O- or a group represented by the formula -CONH-, X represents a hydrogen atom, an alkali metal atom, 1/2(alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having 2 to 22 carbon atoms in total, a trialkanolammonium group having 3 to 22 carbon atoms in total, or a protonated basic amino acid, and l is a number of 2 to 15); or a fatty acid amide derivative represented by the following formula (9):

(wherein R represents a straight-chain or branched alkyl group having 7 to 21 carbon atoms, and R⁵ and R⁶ may be the same or different from each other and each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a group represented by the formula -(C₂H₄O)kH (wherein k is a number of 2 to 4). In the above-mentioned formula (7), R¹ is a straight-chain or branched alkyl group having 8 to 18 carbon atoms, a straight-chain or branched alkenyl group having 8 to 18 carbon atoms, or a substituted phenyl group having a straight-chain or branched alkyl group having 8 to 18 carbon atoms. An alkyl group having 10 to 14 carbon atoms is preferred, and examples thereof include a decyl group, dodecyl group and tetradecyl group. R² is an alkylene group having 2 to 4 carbon atoms. As R², an ethylene group or a propylene group is preferred.

G is a residue derived from a reducing sugar with 5 to 6 carbon atoms. Its structure depends on the chemical structure of the monosaccharide or polysaccharide used as starting material.

Examples of the starting material of the sugar surfactant represented by the above formula (7) (hereinafter referred to as "sugar surfactant (7)") providing the residue represented by G include monosaccharides such as glucose, galactose, fructose, xylose, mannose, lyxose and arabinose, polysaccharides such as maltose, xylobiose, isomaltose, cellobiose, gentiobiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose and melezitose, and mixtures thereof. Of these, glucose, galactose and fructose are particularly preferred.

In the formula (7), m is a number from 0 to 10, preferably 0 to 2. In the formula (7), n is an average sugar polymerization degree and is a number from 1 to 10, which is preferably determined taking into account the polymerization rate obtained by the functional group, R¹. properties. For example, when R¹ is a hydrophobic group having 8 to 11 carbon atoms, n is preferably in the range of 1 to 1.4; and when R¹ is a hydrophobic group having 12 to 14 carbon atoms, n is preferably in the range of 1.5 to 4.0. The average sugar polymerization degree n is determined by ¹H-NMR spectroscopy.

Of the sugar surfactants (7), alkylpolyglucosides in which m is 0 and G is a residue derived from glucose, in other words those represented by the formula R¹-Gn, are particularly preferred.

In the cleaning composition of the present invention, the sugar surfactant (7) may be used singly, or a plurality thereof may be used in combination.

In the cleaning composition of the present invention comprising the glycine derivative (1) and the sugar surfactant (7), the amount of the glycine derivative (1), which depends on, for example, the form of the cleaning composition, is preferably 2 to 60% by weight, particularly preferably 5 to 50% by weight, based on the total weight of the composition. Such cleaning compositions exhibit excellent foaming and provide a clean feeling after washing. The amount of the sugar surfactant (7), which depends on, for example, the form of the cleaning composition, is preferably 2 to 60% by weight, particularly preferably 5 to 50% by weight, based on the total weight of the composition. Such cleaning compositions exhibit excellent foaming and are also improved in storage stability at low temperatures.

The weight ratio of the glycine derivative (1) to the sugar surfactant (7) is preferably 1:30 to 30:1, more preferably 1:10 to 10:1, and most preferably 1:1 to 4:1.

In the above-mentioned formula (8), R3 is a straight-chain or branched alkyl group having 5 to 21 carbon atoms or a straight-chain or branched alkenyl group having 5 to 21 carbon atoms. A straight-chain or branched alkyl group having 11 to 15 carbon atoms and a straight-chain or branched alkenyl group having 11 to 15 carbon atoms are preferred. In the formula (8), l, which represents an average number of oxyethylene groups, is a number of 2 to 15, with a number of 2 to 8 being preferred. The ether type acetic acid surfactant represented by the above-mentioned formula (8) in which l exceeds 15 is poor in foaming ability.

On the other hand, one in which 2 is less than 2 cannot give rise to a composition containing the same in high concentration.

Preferred examples of the ether type acetic acid surfactants represented by formula (8) (hereinafter referred to as "ether type acetic acid surfactant (8)") include polyoxyethylene (2)-lauryl ether acetic acid (R³ = C₁₂H₂₅, Z = -O-, l = 2 and X = H in formula (8)); polyoxyethylene (8)-myristyl ether acetic acid (R³ = C₁₄H₂₈, Z = -O-, l = 8 and X = H in formula (8)); mono(polyoxyethylene (3)-lauramide ether)methanecarboxylic acid (R³ = C₁₁H₂₃, Z = -CONH-, l = 3 and X = H in formula (8)); Mono(polyoxyethylene (6)-lauramide ether)methanecarboxylic acid (R³ = C₁₁H₂₃, Z = -CONH-, l = 6 and X = H in formula (8)); mono(polyoxyethylene (2)-lauramide ether)methanecarboxylic acid (R³ = C₁₁H₂₃, Z = -CONH-, l = 2 and X = H in formula (8)); and salts thereof. Those having a degree of neutralization of 60 to 120% are preferred. It is preferred that the counter ion X is an alkali metal, particularly a potassium atom or sodium atom. And it is preferred that the counter ion X is identical with M₁ and/or M₂ of the glycine derivative (1) used simultaneously.

In the cleaning composition of the present invention, the ether type acetic acid surfactant (8) may be used singly or a plurality thereof may be used in combination.

In the cleaning composition of the present invention comprising the glycine derivative (1) and the ether-type acetic acid surfactant (8), the amount of the glycine derivative (1), which depends on, for example, the form of the cleaning composition, is preferably 2 to 60% by weight, particularly preferably 5 to 50% by weight, based on the total weight of the composition. Such cleaning compositions exhibit excellent foaming and provide a clean feeling after washing. The amount of the ether-type acetic acid surfactant (8), which depends on, for example, the form of the cleaning composition, is preferably 2 to 60% by weight, particularly preferably 5 to 50% by weight, based on the total weight of the composition. Such cleaning compositions exhibit excellent foaming and are also improved in storage stability at low temperatures.

The weight ratio of the glycine derivative (1) to the ether type acetic acid surfactant is preferably 100:1 to 1:2, more preferably 50:1 to 1:1, and particularly preferably 10:1 to 2:1.

In the above-mentioned formula (9), R⁴ is a straight-chain or branched alkyl group having 7 to 21 carbon atoms. A straight-chain or branched alkyl group having 12 to 18 carbon atoms, e.g. a dodecyl group, tridecyl group, tetradecyl group, pentadecyl group or heptadecyl group is particularly preferred. With respect to R⁵ and R⁶, it is preferred that both are hydroxyalkyl groups, particularly hydroxyethyl groups, or that one is a hydroxyalkyl group, particularly hydroxyethyl group, while the other is a hydrogen atom.

Preferred examples of the fatty acid amide derivatives represented by the above-mentioned formula (9) (hereinafter referred to as "fatty acid amide derivative (9)") include lauroylmonoethanolamide, lauroyldiethanolamide, coconut fatty acid monoethanolamide, coconut fatty acid diethanolamide, lauroylmonoisopropanolamide and coconut fatty acid monoisopropanolamide.

In the cleaning composition of the present invention, the fatty acid amide derivative (9) may be used singly or a plurality thereof may be used in combination.

In the cleaning composition of the invention comprising the glycine derivative (1) and the fatty acid amide derivative (9), the amount of the glycine derivative (1), which depends on the form of the cleaning composition, for example, is preferably 2 to 60% by weight, particularly preferably 5 to 50% by weight, based on the total weight of the composition. Such cleaning compositions exhibit excellent foaming and give a clean feeling after washing. The amount of the fatty acid amide derivative (9), which depends on the form of the cleaning composition, for example, is preferably 0.1 to 10% by weight, particularly preferably 1 to 5% by weight, based on the total weight of the composition. Such cleaning compositions produce a very creamy lather.

The weight ratio of the glycine derivative (1) to the fatty acid amide derivative (9) is preferably 100:1 to 2:1, especially 50:1 to 5:1. The sum of the glycine derivative (1) and the fatty acid amide derivative (9), which depends, for example, on the form of the cleaning composition, is preferably, with respect to the total weight of the composition, 5 to 50% by weight in the case of a liquid cleaning composition, 15 to 70% by weight in the case of a paste-like cleaning composition, and 40 to 95% by weight in the case of a solid cleaning composition. The cleaning composition according to the invention may contain other conventional components of cleaning compositions for hair, body and tableware, as long as the presence of such components is not detrimental to the effect according to the invention. Examples of such other components include anionic surfactants (e.g., alkyl sulfate salts, polyoxyethylene alkyl ether sulfate salts, alkylbenzene sulfonates, higher fatty acid salts, α-olefin sulfonates, alkyl sulfonates, N-alkylcarbamylalkanol sulfate salts, N-alkanoylethanolamide sulfate salts, fatty acid glyceride sulfate, alkylglyceryl ether sulfates, taurine surfactants, sarcosine surfactants, isethionate surfactants, and N-acylated acidic amino acid surfactants), amphoteric surfactants (such as, alkyl betaine surfactants, carbamylpropyl betaine surfactants, imidazolinium betaine surfactants, sulfobetaine surfactants, phosphobetaine surfactants, and amino acid surfactants, e.g., sodium laurylaminopropionate), nonionic surfactants (such as, polyoxyethylene alkyl ethers,

polyoxyethylene fatty acid esters, monofatty acid esters of glycerin, fatty acid sorbitan esters and alkyl polyglycosides), cationic surfactants (e.g. alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and ethyl(lanolin fatty acid)aminopropylethyldimethylammonium sulfate), humectants (such as glycerin, propylene glycol and ethylene glycol), thickeners, disinfectants, antiseptics, emulsifiers, polymers (such as carboxyethylcellulose, hydroxyethylcellulose and cationized cellulose) and fragrances.

When the cleaning composition of the present invention contains the glycine derivative (1) and the sugar surfactant (7), the ether-type acetic acid surfactant (8) or the fatty acid amide derivative (9) as essential components, the composition may contain, as long as the presence of such a surfactant is not detrimental to the effect of the present invention, a surfactant other than those described above, for example, an anionic surfactant such as an N-acyl sarcosine salt, an alkyl ether sulfate or a polyoxyethylene alkyl ether sulfate, a nonionic surfactant such as a polyoxyethylene alkyl ether, a sugar ester surfactant or a sugar amide surfactant, or an amphoteric surfactant such as an imidazoline surfactant or a betaine surfactant. In addition, the cleaning composition may contain, as long as the presence of such components is not detrimental to the effect of the invention, other conventional components of cleaning compositions, e.g. viscosity modifiers such as carboxyvinyl polymer, methylcellulose, ethanol and a polyoxyethylene glycol distearate, pearlizing agents, fragrances, colorants, ultraviolet absorbers, antioxidants, disinfectants, anti-inflammatory agents or antiseptics.

It is preferable that the pH of an aqueous solution obtained by diluting 10 times by weight of a cleaning composition of the present invention with water is in the range of 4 to 9, particularly 4 to 6.5. An acid or a base may be added to the cleaning composition during the preparation thereof, or equimolar ion exchange of the glycine derivative (1) may be carried out to adjust the pH thereof to the desired value.

The cleaning composition of the present invention can be prepared according to conventional methods. The form of the cleaning composition is not particularly limited, and examples of the form include liquid, paste, cream, solid and powdery forms. It is particularly preferred that the cleaning composition be in the form of a liquid, paste or cream. When a liquid cleaning composition is prepared, water is preferably used as a liquid medium. The amount of water contained in the liquid cleaning composition is preferably 5 to 90% by weight based on the total weight of the composition.

The cleaning composition of the present invention exhibits excellent foaming and foam stability during washing, exhibits excellent foam breaking and is not slimy and sticky during rinsing, exhibits reduced skin irritation, and is excellent in terms of storage stability at low temperature.

The cleaning composition according to the invention can be used to clean the hair and/or body as well as articles, such as dishes. In such methods, a composition of the invention is applied to the hair, skin or article for a period of time sufficient to effect cleaning of the hair, skin or article and then rinsed from the hair, skin or article with water. The cleaning composition of the invention is useful as a body cleansing composition, such as skin and hair, particularly as a skin cleansing composition. Although it is preferred that the hair or skin be human, the compositions of the invention can also be used to wash the hair or skin of animals, such as cats, dogs, etc. Other features of the invention will become apparent from the following descriptions of exemplary embodiments which are given to illustrate the invention and are not intended to be limiting thereof.

EXAMPLES EXAMPLE 1 Sodium N-cyanoethylglycinate:

150.77 g (2.0084 mol) of glycine and 100 mL of water were charged into a 1 L four-necked flask equipped with a stirrer, a thermometer and a dropping funnel. 200 mL of an aqueous solution of 80.46 g (2.0115 mol) of NaOH was added thereto with stirring to thereby obtain an aqueous sodium glycinate solution. Then, 106.7 g (2.0109 mol) of acrylonitrile was added to this solution over a period of about 30 minutes with stirring. was added dropwise. During the dropwise addition, the reaction system was kept at a temperature of 40 to 70°C. Thereafter, the reaction mixture was stirred at 60°C for 2 hours to complete the reaction. After the reaction was completed, the reaction system was cooled to room temperature. Thus, 568 g (yield: 97.8%) of a 51.9% aqueous solution of sodium cyanoethylglycinate was obtained. A portion of this was taken out, dehydrated and dried to obtain a colorless powder. The powder was subjected to the following analyses. As a result, it was confirmed that the obtained product was a compound represented by the following formula:

1 H NMR spectrum (200 MHz, D2 O): shown in Figure 1 3.21 (s, 2H), 2.90 (t, 2H), 2.68 (t, 2H) ppm elemental analysis (C5 H7 N2 O2 Na = 150.11)

Calculated (%): C 40.01 H 4.70 N 18.66 O 21.32

Found (%): 40.01 4.68 18.80 21.41

EXAMPLE 2 N-Cyanoethyl-N-dodecanoylglycine:

222.4 g (0.7689 mol) of the 51.9% aqueous solution of sodium N-cyanoethylglycinate obtained in Example 1 and 50 ml of acetone were charged into a 1-liter four-necked flask equipped with a stirrer, a thermometer and a dropping funnel, and cooled with ice. Then, 183.9 g (0.8406 mol) of dodecanoyl chloride was added dropwise to this solution over a period of 1 hour with stirring. During the dropwise addition, the reaction system was maintained at a pH of 9 to 11 by dropwise adding a 40% aqueous solution of NaOH while maintaining the temperature at 10 to 25°C. After completion of the dropwise addition of the dodecanoyl chloride, the reaction mixture was stirred at room temperature for 2 hours. Thereafter, the pH of the reaction mixture was adjusted to 1.2 with concentrated hydrochloric acid. A water-insoluble component in the reaction mixture was extracted with chloroform. The obtained organic phase was concentrated and dried sufficiently. Thus, 228.99 g (yield: 95.9%) of a colorless powder of N-cyanoethyl-N-dodecanoylglycine represented by the following formula was obtained. The acid value thereof was 189.2 (calculated: 180.73).

Infrared absorption spectrum (KBr):

2928 (s), 2856 (s), 2244 (w), 1740 (s), 1606 (s), 1184 (s) cm⁻¹

1 H NMR spectrum (200 MHz, CDCl3 ): shown in Figure 2 4.20 (s, 1H), 4.11 (s, 1H), 3.72 (t, 1H), 3.63 (t , 1H), 2.68 (t, 1H), 2.66 (t, 1H), 2.42 (t, 1H), 2.25 (t, 1H), 1.61 (m, 2H), 1 .26 (b, 16H), 0.86 (t, 3H) ppm

Elemental analysis (C17 H30 N2 O3 = 310.44)

Calculated (%): C 65.77 H 9.74 N 9.02 O 15.46

Found (%): 65.63 9.76 8.99 15.53

EXAMPLE 3 Sodium N-cyanoethyl-N-dodecanoyl glycinate:

Sodium N-cyanoethylglycinate was acylated using dodecanoyl chloride and a 48% aqueous solution of NaOH in the same manner as in Example 2. The pH of the resulting aqueous solution of the reaction mixture was adjusted to 7.0 with concentrated hydrochloric acid. The obtained aqueous solution was desalted using an electrodialyzer to thereby reduce the salt concentration to 2% or less. Thereafter, the water was evaporated using a rotary evaporator and the residue was washed with acetone to obtain sodium N-cyanoethyl N-dodecanoylglycinate as a colorless powder.

Infrared absorption spectrum (KBr):

2928 (s), 2856 (s), 2260 (f), 1638 (s), 1622 (s), 1560 (f), 1470 (m), 1422 (m), 1400 (m), 1384 (m), 1318 (m), 718 (w) cm⁻¹

1 H NMR spectrum (200 MHz, D2 O):

4.02 (s, 1H), 3.94 (s, 1H), 3.76 (t, 1H), 3.65 (t, 1H), 2.80 (t, 1H), 2.71 (t , 1H), 2.50 (t, 1H), 2.30 (t, 1H), 1.60 (m, 2H), 1.31 (b, 16H), 0.89 (t, 3H) ppm

EXAMPLE 4 Potassium N-cyanoethyl-N-dodecanoyl glycinate:

A 30% aqueous solution of KOH was gradually added to the N-cyanoethyl-N-dodecanoylglycine obtained in Example 2 to thereby adjust the pH of the system to 6.0. Thus, an aqueous solution of potassium N-cyanoethyl-N-dodecanoylglycinate was obtained.

¹H-NMR spectrum (200 MHz, D20):

4.02 (s, 1H), 3.94 (s, iH), 3.76 (t, 1H), 3.65 (t, 1H), 2.80 (t, 1H), 2.71 (t , 1H), 2.50 (t, 1H), 2.30 (t, 1H), 1, 60 (m, 2H), 1.31 (b, 16H), 0, 89 (t, 3H) ppm

EXAMPLE 5 Ammonium N-cyanoethyl-N-dodecanoyl glycinate:

28% aqueous ammonia was gradually added to the N-cyanoethyl-N-dodecanoylglycine obtained in Example 2 to thereby adjust the pH of the system to 6.5. Thus, an aqueous solution of ammonium N-cyanoethyl-N-dodecanoylglycinate was obtained.

¹H-NMR spectrum (200 MHz, D20):

4.02 (s, 1H), 3, 94 (s, 1H), 3, 76 (t, 1H), 3, 65 (t, 1H), 2.80 (t, 1H), 2.71 (t , 1H), 2.50 (t, 1H), 2.30 (t, 1H), 1.60 (m, 2H), 1.31 (b, 16H), 0.89 (t, 3H) ppm

EXAMPLE 6 N-Carboxyethyl-N-dodecanoylglycine:

110.18 g (0.3549 mol) of N-cyanoethyl-N-dodecanoylglycine obtained in Example 2 and 200 ml of water were charged into a 1-L four-necked flask equipped with a stirrer, a thermometer and a cooling tube, and cooled with ice. Then, 200 ml of an aqueous solution of 58.6 g (0.888 mol) of KOH was added thereto with stirring. The resulting solution was stirred at 90 °C for 2 hours. Thereafter, the solution was cooled to room temperature and the pH thereof was adjusted to 1.5 with concentrated hydrochloric acid. A water-insoluble component in the reaction mixture was extracted with chloroform, and the obtained organic phase was concentrated and sufficiently dried. Thus, 113.71 g (yield 97.3%) of a colorless powder of N-carboxyethyl-N-dodecanoylglycine represented by the following formula was obtained:

Infrared absorption spectrum (KBr):

3150 (b), 2924 (s), 2860 (s), 1724 (s), 1616 (s), 1478 (s), 1418 (m), 1258 (s), 1188 (s) cm⁻¹

1 H-NMR spectrum (200 MHz, CDCl3 ): shown in Fig. 3 10, 4 (b, 2H), 4, 19 (s, 1H), 4, 17 (s, 1H), 3, 67 (dd , 2H), 2, 65 (t, 2H), 2, 33 (t, 1H), 2.12 (t, 1H), 1, 58 (m, 2H), 1.23 (b, 16H), 0 .80 (t, 3H) ppm

Mass spectrum (FAB ionization method, negative) m/z = 679 (2M+Na-2), 328 (M-1), 256 (base), 212

Elemental analysis (C17 H31 NO5 = 329.44)

Calculated (%): C 61.98 H 9.48 N 4.25 O 24.28 Found (%): 62.06 9.48 4.09 24.31

EXAMPLE 7 Disodium N-carboxyethyl glycinate:

80.00 g (1.0657 mol) of glycine and 160 ml of an aqueous solution of 42.63 g (1.066 mol) of NaOH were charged into a 2-L four-necked flask equipped with a stirrer, a thermometer and a dropping funnel, and heated with stirring. Then, 59.38 g (1.119 mol) of acrylonitrile was added dropwise to this solution over a period of about 30 minutes with stirring. During the dropping, the reaction system was kept at a temperature of 40 to 60 °C. After the dropping was completed, the reaction mixture was stirred at 60 °C for 1 hour. 300 ml of an aqueous solution of 63.95 g (1.5988 mol) of NaOH was added thereto with stirring. Thereafter, the temperature was raised to 80 °C and the reaction solution was stirred for 2 hours. During this period, nitrogen gas was blown into the reaction solution, whereby ammonia gas generated was continuously removed from the system. After completion of the reaction, the reaction system was cooled to room temperature. Thus, disodium N-carboxyethylglycinate represented by the following formula was obtained. A portion of this was taken out, dehydrated and dried to obtain a colorless powder.

Infrared absorption spectrum (KBr):

3420 (b), 2952 (w), 2820 (w), 1584 (s), 1424 (s) cm⁻¹

1 H NMR spectrum (200 MHz, D2 O): shown in Figure 4 3.15 (s, 2H), 2.72 (t, 2H), 2.37 (t, 2H) ppm

EXAMPLE 8 N-Carboxyethyl-N-dodecanoylglycine:

150 ml of acetone was added to the aqueous solution of disodium N-carboxyethylglycinate obtained in Example 7 with continuous stirring. Then, 228.29 g (1.0435 mol) of dodecanoyl chloride was added dropwise to this solution over a period of 1.5 hours with stirring. During this period, the reaction system was maintained at a pH of 9 to 11 by dropwise addition of a 40% aqueous solution of NaOH while maintaining the temperature at 10 to 25°C. After completion of the dropwise addition, the reaction mixture was stirred at room temperature for 2 hours. Thereafter, the pH of the reaction mixture was adjusted to 1.2 with concentrated hydrochloric acid. A white precipitate formed was separated by filtration, washed with water and dried to obtain 324.71 g (yield starting from glycine: 92.5%) of a white powder of N-carboxyethyl-N-dodecanoylglycine. The infrared absorption spectrum, 1H-NMR spectrum, mass spectrum and elemental analysis results were the same as those in Example 6.

EXAMPLE 9 Sodium N-carboxyethyl N-dodecanoyl glycinate:

Disodium N-carboxyethylglycinate was acylated using dodecanoyl chloride and a 48% aqueous solution of NaOH in the same manner as in Example 8. The pH of the resulting aqueous solution of the reaction mixture was adjusted to 7.0 with concentrated hydrochloric acid. The obtained aqueous solution was desalted using an electrodialyzer, thereby reducing the salt concentration to 2% or less. Thereafter, the water was evaporated using a rotary evaporator, and the residue was washed with acetone to obtain sodium N-carboxyethyl N-dodecanoylglycinate (the term "sodium" includes monosodium, disodium, and a mixture of monosodium and disodium) as a colorless powder.

Infrared absorption spectrum (KBr):

2928 (s), 2856 (s), 1650 (s), 1630 (s),1606 (s), 1588 (s), 1482 (m), 1464 (s), 1442 (s), 1422 (s), 1406 (s), 1360 (m), 1306 (m) cm⁻¹

1 H NMR spectrum (200 MHz, D2 O):

3.96 (s, 1H), 3.89 (s, ZH), 3.59 (m, 2H), 2.44 (m, 3H), 2.28 (t, 1H), 1.57 (m , 2H), 1.30 (b, 16H), 0.90 (t, 3H) ppm

EXAMPLE 10 Potassium N-carboxyethyl N-dodecanoyl glycinate:

80.50 g (1.0723 mol) of glycine and 150 ml of an aqueous solution of 60.20 g (1.073 mol) of KOH were charged into a 2-L four-necked flask equipped with a stirrer, a thermometer and a dropping funnel, and heated with stirring. Then, 56.90 g (1.072 mol) of acrylonitrile was added dropwise to this solution over a period of about 30 minutes with stirring. During this period, the reaction system was maintained at a temperature of 45 to 55°C. After completion of the dropping, the reaction mixture was stirred at 55°C for 1 hour, and the temperature was lowered to room temperature. Subsequently, 120 ml of water and 90 ml of acetone were added to the reaction solution thus obtained, and then 234.50 g (1.0719 mol) of dodecanoyl chloride was added dropwise thereto over a period of 1 hour with stirring. During this period, the reaction system was maintained at a pH of 9 to 11 by dropwise addition of a 30% aqueous solution of KOH while maintaining the temperature at 5 to 25°C. After completion of the dropwise addition of dodecanoyl chloride, the resulting reaction mixture was stirred at room temperature for 2 hours. Then, a 30% aqueous solution of KOH was further added in such an amount that the sum of the amount of KOH and the amount previously added for pH adjustment became 150.00 g (2.673 mol). Thereafter, the reaction solution thus obtained was stirred at 80°C for 2 hours. During this period, nitrogen gas was blown into the reaction solution, whereby ammonia gas was continuously removed from the system. The reaction solution was then cooled to room temperature, and then the pH of the system was adjusted to 6.0 with concentrated hydrochloric acid. The resulting aqueous solution was desalted using an electrodialyzer. Thus, potassium Ncarboxyethyldodecanoylglycinate (the term "potassium" includes monopotassium, dipotassium and a mixture of monopotassium and dipotassium) was obtained in the form of an aqueous solution.

1 H NMR spectrum (200 MHz, D2 O):

3.96 (s, 1H), 3.89 (s, 1H), 3.59 (m, 2H), 2.44 (m, 3H), 2.28 (t, 1H), 1.57 (m , 2H), 1.30 (b, 16H), 0.90 (t, 3H) ppm

EXAMPLE 11 Magnesium N-carboxyethyl N-dodecanoyl glycinate:

To the N-carboxyethyl-N-dodecanoylglycine obtained in Example 8, distilled water was added in a volume 3 times that of the N-carboxyethyl-N-dodecanoylglycine. Then, the resulting suspension was heated to 40°C with stirring. Powdery Mg(OH)2 was gradually added thereto with stirring to thereby adjust the pH of the system to 6.0. Thus, an aqueous solution of magnesium N-carboxyethyl-N-dodecanoylglycinate (the term "magnesium" includes 1/2(magnesium), magnesium and a mixture of 1/2(magnesium) and magnesium) was obtained.

1 H NMR spectrum (200 MHz, D2 O):

3.96 (s, 1H), 3.89 (s, 1H), 3.59 (m, 2H), 2.44 (m, 3H), 2.28 (t, 1H), 1.57 (m , 2H), 1.30 (b, 16H), 0.90 (t, 3H) ppm

EXAMPLE 12 Ammonium N-carboxyethyl N-dodecanoyl glycinate:

28% aqueous ammonia was gradually added to the N-carboxyethyl-N-dodecanoylglycine obtained in Example 8 to thereby adjust the pH of the system to 6.5. Thus, an aqueous solution of ammonium N-carboxyethyl-N-dodecanoylglycinate (the term "ammonium" includes monoammonium, diammonium and a mixture of monoammonium and diammonium) was obtained.

1 H NMR spectrum (200 MHz, D2 O):

3.96 (s, 1H), 3.89 (s, 1H), 3.59 (m, 2H), 2.44 (m, 3H), 2.28 (t, 1H), 1.57 (m , 2H), 1.30 (b, 16H), 0.90 (t, 3H) ppm

EXAMPLE 13 N-Carboxyethyl-N-tetradecanoylglycine:

50.01 g (0.6662 mol) of glycine and 100 ml of an aqueous solution of 26.68 g (0.667 mol) of NaOH were charged into a 2-liter four-necked flask equipped with a stirrer, a thermometer and a dropping funnel, and heated with stirring. Then, 37.23 g (0.7017 mol) of acrylonitrile was added dropwise to this solution over a period of about 20 minutes with stirring. During the dropping, the reaction system was kept at a temperature of 40 to 50°C. After the dropping was completed, the reaction mixture was stirred at 50°C for 1 hour, and the temperature was lowered to room temperature. Then, 200 ml of water and 120 ml of acetone were added to the reaction mixture thus obtained. and 164.91 g (0.6681 mol) of tetradecanoyl chloride were added dropwise thereto over a period of 1 hour with stirring. During the dropwise addition of tetradecanoyl chloride, the reaction system was maintained at a pH of 9 to 11 by dropwise addition of a 30% aqueous solution of NaOH while maintaining the temperature at 5 to 30°C. After completion of the dropwise addition, the reaction mixture was stirred at room temperature for 1 hour. Then, 50 ml of ethanol and a 30% aqueous solution of NaOH were added thereto. The 30% aqueous solution of NaOH was added in such an amount that the amount of NaOH and the amount previously added for pH adjustment became 75.67 g (1.892 mol). Thereafter, the reaction solution was stirred at 90°C for 3 hours. During this period, nitrogen gas was blown into the reaction solution to continuously remove ammonia gas generated from the system. After that, the reaction solution was cooled to room temperature and the pH was adjusted to 1.0 with concentrated hydrochloric acid. A white precipitate formed was separated by filtration, washed with water and dried. Thus, 229.16 g (yield, starting from glycine: 96.2%) of a white powder of N-carboxyethyl-N-tetradecanoylglycine represented by the following formula was obtained:

Infrared absorption spectrum (KBr):

3150 (b), 2924 (s), 2860 (s), 1724 (s), 1616 (s) 1478 (s), 1418 (m), 1258 (s), 1188 (s) cm⁻¹

1 H NMR spectrum (200 MHz, CDCl3 ):

10.4 (b, 2H), 4.19 (s, 1H), 4.17 (s, 1H), 3.67 (dd, 2H), 2.65 (t, 2H), 2.33 (t , 111), 2.12 (t, 1H), 1.58 (m, 2H), I.23 (b, 16H), 0.80 (t, 3H) ppm

Elemental analysis (C19 H35 NO5 = 357.49):

Calculated (%): C 63.84 H 9.87 N 3.92 O 22.38

Found (%): 63.71 9.91 3.90 22.52

TEST EXAMPLE 1

The foaming ability of each of the glycine derivatives of the present invention and a comparative product was evaluated by the following method. The results are shown in Table 1.

Method for evaluating foaming capacity:

A mixture (pH 7.0) of a surfactant (0.1% by weight), lanolin (0.3% by weight) and water (hardness 4º DH) was foamed at 40ºC according to the "Water Flash" method. The volume of the foam was measured 10 seconds and 120 seconds after the foaming was stopped. TABLE 1

TEST EXAMPLE 2

With respect to each of the glycine derivatives of the present invention and the comparative products, skin irritation was evaluated by the following method. The results are shown in Table 2.

Method for assessing skin irritation:

An aqueous surfactant solution (pH 7.0) with a concentration of 10% by weight was applied to the side of a white Hartley guinea pig (6 weeks old, female) whose hair had been trimmed and shaved once a day for four consecutive days, and the skin irritation was evaluated. For evaluation, the part to which the solution was applied was observed 24 hours after the fourth application, and the result of the observation was ranked according to the following criteria. Table 2 shows the average of the ranked evaluations (N = 5).

Criteria:

0: no reaction observed;

1: mild erythema observed;

2: clear erythema observed;

3: clear erythema accompanied by edema observed; and

4: clear erythema accompanied by edema, crust and necrosis observed

TABLE 2

Surfactant Average of rated ratings

Sodium N-carboxyethyl-N- dodecanoylglycinate, obtained in Example 9 0.2

C₁₂H₂₅-(OCH₂CH₂)4.0-OSO₃Na (Comparative product 1) 2.2

C₁₂H₂₅-OSO₃Na (Comparative product 2) 2.6

Formulation examples of the cleaning compositions of the present invention are described below.

FORMULATION EXAMPLE 1

A shampoo (pH 5.0) with the following composition was prepared. The resulting shampoo was not only excellent in terms of foaming ability and detergent power, but also ensured a good feeling when washing and rinsing the hair.

Sodium N-carboxyethyl-N-dodecanoylglycinate obtained in Example 9 15.0 wt.%

Lauroyldiethanolamide 3.0

Lauryldimethylamine oxide 0.5

Hydroxyethylcellulose (SE-850K, manufactured by Daicel Chemical Industries, Ltd.) 0.1

Sodium benzoate appropriate amount

Citric acid appropriate amount

Dye appropriate amount

Fragrance appropriate amount

Water Rest

total: 100% by weight

FORMULATION EXAMPLE 2

A shampoo (pH 4.5) with the following composition was prepared. The resulting shampoo was not only excellent in terms of foaming ability and detergent power, but also ensured a good feeling when washing and rinsing the hair.

Sodium N-carboxyethyl-N-dodecanoylglycinate obtained in Example 9 10.0 wt.%

Sodium N-cyanoethyl-N-dodecanoylglycinate obtained in Example 3 5.0

Lauroyldiethanolamide 3.0

Lauryldimethylamine oxide 0.5

Hydroxyethylcellulose (SE-850K, manufactured by Daicel Chemical Industries, Ltd.) 0.1

Sodium benzoate appropriate amount

Phosphoric acid appropriate amount

Dye appropriate amount

Fragrance appropriate amount

Water Rest

total: 100% by weight

FORMULATION EXAMPLE 3

A body shampoo (pH 6.0) with the following composition was prepared. The obtained body shampoo was excellent in foaming ability and detergency and ensured a refreshing and good feeling during washing and rinsing and after washing.

Ammonium N-carboxyethyl-N- dodecanoylglycinate obtained in Example 12 15.0 wt.%

Lauryldimethylacetic acid betaine 3.0

Lauric acid 0.5

Sucrose fatty acid esters 0.1

Sodium benzoate appropriate amount

Citric acid appropriate amount

Methylparaben appropriate amount

Dye appropriate amount

Fragrance appropriate amount

Water Rest

total: 100% by weight

FORMULATION EXAMPLE 4

A body shampoo (pH 5.0) with the following composition was prepared: The obtained body shampoo was excellent in foaming ability and detergency and ensured a refreshing and good feeling during washing and rinsing and after washing.

Sodium N-carboxyethyl-N- dodecanoylglycinate obtained in 10.0 Example 9 wt.%

Sodium N-cyanoethyl-N-dodecanoylglycinate obtained in Example 3 5.0

Lauryldimethylamine oxide 3.0

Lauric acid 0.5

Sucrose fatty acid esters 0.1

Sodium benzoate appropriate amount

Citric acid appropriate amount

Methylparaben appropriate amount

Dye appropriate amount

Fragrance appropriate amount

Water Rest

total: 100% by weight

TEST EXAMPLE 3

The components of each of the cleaning compositions shown in Tables 3 and 4 were homogeneously mixed in the proportions shown therein, and the pH values of the resulting mixtures were adjusted with hydrochloric acid to prepare cleaning compositions. The pH value of each cleaning composition was determined by diluting it 10 times with water based on the weight of the composition to prepare an aqueous solution, taking 50 ml and measuring the pH value thereof at 25°C using a pH meter F-14 manufactured by Horiba.

The storage stability, foaming and comfort of use of each of the obtained.

Cleaning compositions were evaluated according to the following criteria. The results are shown in Tables 3 and 4.

Evaluation procedure: (i) Storage stability:

50 ml of each cleaning composition was placed in a screw-top glass tube, sealed and stored in a thermostatic chamber at 5ºC for one month. At the end of this period, the liquid state of the contents was visually observed and evaluated according to the following criteria:

O: the liquid was homogeneous and transparent and

X: Crystals have formed or the liquid was cloudy

(ii) Foaming:

Each of the cleaning compositions was diluted 10 times with water to obtain an aqueous solution, and 100 ml (solution temperature: 40ºC) of the aqueous solution was poured into a measuring cylinder. Then, a stirring blade was placed in the aqueous solution and rotated. The stirring blade was rotated at 1000 rpm, and its rotation direction was reversed every 5 seconds. The volume (ml) of the foam formed 30 seconds after the start of stirring was measured and defined as the foam volume, which was evaluated by the following criterion.

: Foam volume of 200 ml or more

O: Foam volume of not less than 160 ml but less than 200 ml

Δ: foam volume of not less than 120 ml, but less than 160 ml and

X: less than 120 ml

(iii) Ease of use:

Organoleptic evaluations on the following items were conducted by having 10 panelists (men and women) perform body cleansing for 1 week using each of the cleansing compositions. The evaluations were conducted according to the following criteria and the average values were calculated. When the average value was 4.5 or more, 3.5 to 4.4, 2.5 to 3.4 and 2.4 or less, the cleansing composition was evaluated as excellent ( ), good (O), normal (Δ) and poor (X) in terms of ease of use, respectively.

(1) Foaming:

5: good foaming

4: relatively good foaming

3: normal

2: relatively poor foaming

1: poor foaming

(2) Foam stability:

5: good foam stability

4: relatively good foam stability

3: normal

2: relatively poor foam stability

1: poor foam stability

(3) Foam breaking during rinsing:

5: good foam breaking

4: relatively good foam breaking

3: normal

2: relatively poor foam breaking

1: poor foam breaking

(4) Clean feeling at the time of towel drying:

5: clean

4: relatively clean

3: normal

2: relatively slimy and sticky

1: slimy and sticky TABLE 3

Note *: may be in the form of monosalt, disalt or a mixture of monosalt and disalt TABLE 4

Note *: can be in the form of monosalt, disalt or a mixture of monosalt and disalt

The cleaning compositions of the present invention were excellent in storage stability, foaming and ease of use, as is clear from the results shown in Tables 3 and 4. Furthermore, they were also excellent in detergency, and their skin irritation was extremely low. Formulation examples of the cleaning compositions of the present invention are described below.

FORMULATION EXAMPLE 5 - Whole Body Cleanser

Components:

(1) Sodium N-carboxyethyl N-dodecanoyl glycinate * 20% by weight

(2) Alkyl saccharide (R¹=C₁₀H₂₁, m = 0, G = glucose and n = 11 in formula (7)) 5

(3) Methyl cellulose 0.1

(4) Fragrance 0.5

(5) Ethanol 3

(6) Sodium hydroxide 2

(7) purified water residue

total 100 wt.%

*: can be in the form of moon salt, disalt or a mixture of monosalt and disalt

Production method:

Components (1) and (6) were added to hot purified water (7) and dissolved therein. After cooling the resulting aqueous solution, components (2) to (5) were added thereto, thereby obtaining a transparent liquid cleaning composition was obtained. The pH of an aqueous solution obtained by diluting the resulting cleaning solution 10 times by weight with water was 6.0.

When the obtained liquid cleansing composition was used in cleansing skin and hair, the cleansing composition was excellent in foaming and rinsability, gave a clean feeling, and was excellent in comfort of use. In addition, its skin irritation was low and its storage stability was excellent.

FORMULATION EXAMPLE 6 - Facial Cleanser

Components:

(1) N-carboxyethyl-N-dodecanoylglycine 20% by weight

(2) Arginine 12

(3) Alkyl saccharide (R¹ = C₁₀H₂₁, m = 0, G = glucose and n = 11 in formula (7)) 10

(4) Lauryldimethylamine oxide 3

(5) Fragrance 0.5

(6) Sodium hydroxide appropriate amount

(7) purified water balance total 100 wt.%

Production method:

Component (2) and then component (1) were added to hot, purified water (7) to neutralize and dissolve. After After cooling the resulting aqueous solution, components (3) to (5) were added thereto, thereby obtaining a transparent liquid cleaning composition. The pH of an aqueous solution obtained by diluting 10 times with water with respect to the weight of the resulting cleaning composition was 6.5.

The use of the obtained liquid cleansing composition in cleansing the face showed that the cleansing composition was excellent in foaming and rinsability, gave a clean feeling, gave no feeling of stiffness after drying, and was also excellent in comfort of use. Furthermore, its skin irritation was low and its storage stability was excellent.

TEST EXAMPLE 4

The components of each of the cleaning compositions shown in Tables 5 and 6 were homogeneously mixed in the indicated proportions, and the pH values of the resulting mixtures were adjusted with hydrochloric acid, thereby preparing the cleaning compositions. The pH value of each cleaning composition was determined by diluting it 10 times with water with respect to the weight of the composition to thereby prepare an aqueous solution, taking 50 ml and measuring the pH value thereof at 25°C using a pH meter F-14 manufactured by Horiba.

The storage stability, foaming and ease of use of each of the obtained cleaning compositions were evaluated. The evaluation methods were the same as in Test Example 3. The results are shown in Tables 5 and 6. TABLE 5

Note *: may be in the form of monosalt, disalt or a mixture of monosalt and disalt TABLE 6

Note *: can be in the form of monosalt, disalt or a mixture of monosalt and disalt

The cleaning compositions of the present invention were excellent in storage stability, foaming and ease of use, as shown in the results shown in Tables 5 and 6. Furthermore, they were also excellent in detergency and their skin irritation was extremely low.

Formulation examples of the cleaning compositions of the present invention are described below.

FORMULATION EXAMPLE 7 - Whole Body Cleanser

Components:

(1) Sodium N-carboxyethyl N-dodecanoyl glycinate * 20% by weight

(2) Sodium salt of mono(polyoxyethylene (2) fatty acid amide ether)- methanecarboxylic acid (aryl group: C₁₂/C₁₄-75 : 25) 5

(3) Methyl cellulose 0.1

(4) Fragrance 0.5

(5) Ethanol 3

(6) Purified water residue

total 100 wt.%

*: can be in the form of monosalt, disalt or a mixture of monosalt and disalt

Production method:

Components (1) and (6) were added to hot purified water (6) and dissolved therein. After cooling the resulting aqueous solution, components (3) to (5) were added thereto, thereby obtaining a transparent liquid cleaning composition. The pH of an aqueous solution obtained by diluting 10 times with water with respect to the weight of the resulting cleaning solution was 6.0.

When the obtained liquid cleansing composition was used in cleansing skin and hair, the cleansing composition was excellent in foaming and rinsability, gave a clean feeling, and was excellent in comfort of use. In addition, its skin irritation was low and its storage stability was excellent.

FORMULATION EXAMPLE 8 - Facial Cleanser

Components:

(1) N-carboxyethyl-N-dodecanoylglycine 15% by weight

(2) N-carboxyethyl-N-tetradecanoylglycine 5

(3) Arginine 8

(4) Sodium salt of mono(polyoxyethylene (4)-laurylamide ether)- methanecarboxylic acid 5

(5) Lauryldimethylamine oxide 3

(6) Fragrance 0.5

(7) purified water residue

total 100 wt.%

Production method:

Component (3) and then components (1) and (2) were added to hot purified water (7) to neutralize and dissolve. After cooling the resulting aqueous solution, components (4) to (6) were added thereto, thereby obtaining a transparent liquid cleaning composition.

The use of the obtained liquid cleansing composition in cleansing the face showed that the cleansing composition was excellent in foaming and rinsability, gave a clean feeling, gave no feeling of stiffness after drying, and was also excellent in comfort of use.

TEST EXAMPLE 5

The components of each of the cleaning compositions shown in Tables 7 and 8 were homogeneously mixed in the indicated proportions, and the pH values of the resulting mixtures were adjusted with hydrochloric acid, thereby preparing the cleaning compositions. The pH value of each cleaning composition was determined by diluting it 10 times with water with respect to the weight of the composition to thereby prepare an aqueous solution, taking 50 ml and measuring the pH value thereof at 25°C using a pH meter F-14 manufactured by Horiba.

The storage stability, foaming and ease of use of each of the obtained cleaning compositions were evaluated. The evaluation methods were the same as in Test Example 3. The results are shown in Tables 7 and 8. TABLE 7

Note *: may be in the form of monosalt, disalt or a mixture of monosalt and disalt TABLE 8

Note * can be in the form of the monosalt, disalt or a mixture of the monosalt and disalt

The cleaning compositions of the present invention were excellent in storage stability, foaming and ease of use, as can be seen from the results shown in Tables 7 and 8. Furthermore, they were also excellent in detergency and their skin irritation was extremely low. Formulation examples of the cleaning compositions of the present invention are described below.

FORMULATION EXAMPLE 9 - Whole Body Cleanser

Components:

(1) Sodium N-carboxyethyl N-dodecanoyl glycinate * 15% by weight

(2) Sodium N-carboxyethyl N-tetradecanoyl glycinate*5

(3) Lauroyldiethanolamide 5

(4) Methyl cellulose 0.1

(5) Fragrance 0.5

(6) Ethanol 3

(7) purified water residue

total 100 wt.%

*: can be in the form of monosalt, disalt or a mixture of monosalt and disalt

Production method:

Components (1) and (2) were added to hot purified water (7) and dissolved therein. After cooling the resulting aqueous solution, components (3) to (6) were added thereto, thereby obtaining a transparent liquid cleaning composition. (whole body cleanser). The pH of an aqueous solution obtained by diluting 10 times with water with respect to the weight of the resulting cleaning solution was 6.0.

When the obtained liquid cleansing composition was used in cleansing skin and hair, the cleansing composition was excellent in foaming and rinsability, gave a clean feeling, and was excellent in comfort of use. In addition, its skin irritation was low and its storage stability was excellent.

FORMULATION EXAMPLE 10 - Facial Cleanser

Components:

(1) N-carboxyethyl-N-dodecanoylglycine 12% by weight

(2) N-carboxyethyl-N-tetradecanoylglycine 8

(3) Arginine 8

(4) Coconut fatty acid monoethanolamide 5

(5) Glycerine 10

(6) Fragrance 0.5

(7) purified water residue

total 100 wt.%

Production method:

Component (3) and then components (1) and (2) were added to hot purified water (7) to neutralize and dissolve. Then components (4) and (5) were added and mixed therewith. After cooling the resulting aqueous solution, the component (6) was added thereto to obtain a transparent liquid cleansing composition (facial cleanser). The pH of an aqueous solution obtained by diluting 10 times with water with respect to the weight of the resulting cleansing solution was 6.0.

Using the obtained facial cleanser in cleansing the face showed that the facial cleanser was excellent in foaming and rinsability, gave a clean feeling, gave no feeling of stiffness after drying, and was also excellent in comfort of use. In addition, its skin irritation was low and its storage stability was excellent.

Claims (23)

1. Glycine derivative represented by the following formula (1): wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ and M₂ are the same or different from each other and each independently represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a trialkanolammonium group having a total of 3 to 22 carbon atoms or a protonated basic amino acid. 2. Glycine derivative according to claim 1, wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms or a straight-chain or branched alkenyl group having 11 to 13 carbon atoms, and M₁ and M₂ are the same or different from each other and each independently represent a hydrogen atom, a sodium atom, a potassium atom, 1/2(magnesium atom), an ammonium group, a monoethanolammonium group, a diethanolammonium group or a triethanolammonium group. 3. The glycine derivative according to claim 1, wherein R represents a straight-chain alkyl group having 11 to 13 carbon atoms, and M₁ and M₂ are the same or different from each other and each represents a hydrogen atom, a sodium atom, a potassium atom or an ammonium group. 4. Glycine derivative represented by the following formula (2): wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ represents a hydrogen atom, an alkali metal atom, 1/2(alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a trialkanolammonium group having a total of 3 to 22 carbon atoms or a protonated basic amino acid. 5. Glycine derivative represented by the following formula (3): wherein M₁ and M₂ are the same or different from each other and each represents 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a trialkanolammonium group having a total of 3 to 22 carbon atoms or a protonated basic amino acid. 6. Glycine derivative represented by the following formula (4): wherein M₁ represents an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a trialkanolammonium group having a total of 3 to 22 carbon atoms or a protonated basic amino acid. 7. A process for producing a glycine derivative represented by the following formula (1): wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ and M₂ are the same or different from each other and each independently represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having 2 to 22 carbon atoms in total, a trialkanolammonium group having 3 to 22 carbon atoms in total, or a protonated basic amino acid, which comprises hydrolyzing the cyano group of a glycine derivative represented by the following formula (2), optionally followed by salt exchange: where R and M₁ are as defined above. 8. A process for producing a glycine derivative represented by the following formula (1): wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ and M₂ are the same or different from each other and each independently represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having 2 to 22 carbon atoms in total, a trialkanolammonium group having 3 to 22 carbon atoms in total or a protonated basic amino acid, which comprises reacting a glycine derivative represented by the following formula (3): wherein M₁ and M₂ are each as defined above, with an acid chloride represented by the following formula (6), and optionally subsequently a salt exchange: RCOCl (6) where R is defined as above. 9. A process for producing a glycine derivative represented by the following formula (2): wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ represents a hydrogen atom, an alkali metal atom, 1/2(alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having 2 to 22 carbon atoms in total, a trialkanolammonium group having 3 to 22 carbon atoms in total or a protonated basic amino acid, which comprises reacting a glycine derivative represented by the following formula (4): wherein M₁ is as defined above, with an acid chloride represented by the following formula (6), and optionally subsequently a salt exchange : RCOCl (6) where R is defined as above. 10. A process for producing a glycine derivative represented by the following formula (3): wherein M₁ and M₂ are the same or different from each other and each represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having 2 to 22 carbon atoms in total, a trialkanolammonium group having 3 to 22 carbon atoms in total, or a protonated basic amino acid, which comprises hydrolyzing the cyano group of a glycine derivative represented by the following formula (4), and optionally then subjecting it to salt exchange: where M₁ is as defined above. 11. A process for producing a glycine derivative represented by the following formula (4): wherein M₁ represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having 2 to 22 carbon atoms in total, a trialkanolammonium group having 3 to 22 carbon atoms in total, or a protonated basic amino acid, which comprises reacting glycine or a salt thereof represented by the following formula (5) with acrylonitrile: where M₁ is as defined above. 12. A process for producing a glycine derivative represented by the following formula (2): wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a trialkanolammonium group having a total of 3 to 22 carbon atoms or a protonated basic amino acid, which comprises a step of reacting glycine or a salt thereof; represented by the following formula (5): wherein M₁ is as defined above, with acrylonitrile to obtain a glycine derivative represented by the following formula (4): wherein M₁ is as defined above, and comprising a step of reacting the glycine derivative represented by the above formula (4) with an acid chloride represented by the following formula (6) and optionally then subjecting it to salt exchange: RCOCl (6) where R is defined as above. 13. A process for producing a glycine derivative represented by the following formula (1): where R is a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ and M₂ are the same or different from each other and each independently represents a hydrogen atom, an alkali metal atom, 1/2(alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having 2 to 22 carbon atoms in total, a trialkanolammonium group having 3 to 22 carbon atoms in total, or a protonated basic amino acid, which comprises a step of reacting glycine or a salt thereof represented by the following formula (5): wherein M₁ is as defined above, with acrylonitrile to obtain a glycine derivative represented by the following formula (4): wherein M1 is as defined above, and comprising a step of hydrolyzing the cyano group of the glycine derivative represented by the above formula (4) and optionally then subjecting it to salt exchange. 14. A process for producing a glycine derivative represented by the following formula (3): wherein M₁ and M₂ are the same or different from each other and each represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having 2 to 22 carbon atoms in total, a trialkanolammonium group having 3 to 22 carbon atoms in total, or a protonated basic amino acid, which comprises a step of reacting glycine or a salt thereof represented by the following formula (5): wherein M₁ is as defined above, with acrylonitrile to obtain a glycine derivative represented by the following formula (4): wherein M1 is as defined above, and comprising a step of hydrolyzing the cyano group of the glycine derivative represented by the above formula (4) and optionally then subjecting it to salt exchange. 15. A process for producing a glycine derivative represented by the following formula (1): wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ and M₂ are the same or different from each other and each independently represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having 2 to 22 carbon atoms in total, a trialkanolammonium group having 3 to 22 carbon atoms in total, or a protonated basic amino acid, which comprises a step of reacting glycine or a salt thereof represented by the following formula (5): wherein M₁ is as defined above, with acrylonitrile to obtain a glycine derivative represented by the following formula (4): wherein M₁ is as defined above, a step of reacting the glycine derivative represented by the above formula (4) with an acid chloride represented by the following formula (6): RCOCl (6) wherein R is as defined above, and optionally subsequently subjecting the glycine derivative to a salt exchange to obtain a glycine derivative represented by the following formula (2): wherein R and M1 are as defined above, and a step of hydrolyzing the cyano group of the glycine derivative represented by the above formula (2) and then optionally subjecting it to salt exchange. 16. A process for producing a glycine derivative represented by the following formula (1): wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ and M₂ are or are different from each other and each independently represents a hydrogen atom, an alkali metal atom, 1/2(alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a trialkanolammonium group having a total of 3 to 22 carbon atoms or a protonated basic amino acid, which comprises a step of reacting glycine or a salt thereof represented by the following formula (5): wherein M₁ is as defined above, with acrylonitrile to obtain a glycine derivative represented by the following formula (4): wherein M₁ is as defined above, a step of hydrolyzing the cyano group of the glycine derivative represented by the above formula (4), optionally followed by salt exchange to obtain a glycine derivative represented by the following formula (3): wherein M₁ and M₂ are each as defined above, and a step of reacting the glycine derivative represented by the above formula (3) with an acid chloride represented by the following formula (6) and optionally then subjecting them to salt exchange: RCOCl (6) where R is defined as above. 17. A cleaning solution comprising a glycine derivative represented by the following formula (1): wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ and M₂ are the same or different from each other and each independently represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a trialkanolammonium group having a total of 3 to 22 carbon atoms or a protonated basic amino acid. 18. The cleaning solution according to claim 17, which further comprises a sugar surfactant represented by the following formula (7): R¹-(OR²)m-Gn (7) wherein R¹ represents a straight-chain or branched alkyl group having 8 to 18 carbon atoms, a straight-chain or branched alkenyl group having 8 to 18 carbon atoms or a substituted phenyl group having a straight-chain or branched alkyl group having 8 to 18 carbon atoms, R² represents an alkylene group having 2 to 4 carbon atoms, G is a radical derived from a reducing sugar having 5 to 6 carbon atoms, m represents a number from 0 to 10 and n represents a number from 1 to 10. 19. The cleaning solution according to claim 17, which further comprises an ether type acetic acid surfactant represented by the following formula (8): R³-Z-(CH₂CH₂O)l-CH₂CO₂X (8) wherein R³ represents a straight-chain or branched alkyl group having 5 to 21 carbon atoms, or a straight-chain or branched alkenyl group having 5 to 21 carbon atoms, Z represents a group represented by the formula -O- or a group represented by the formula -CONH-, X represents a hydrogen atom, an alkali metal atom, 1/2(alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a Trialkanolammonium group with a total of 3 to 22 carbon atoms or a protonated basic amino acid, and l is a number from 2 to 15. 20. A cleaning composition according to claim 17, which further comprises a fatty acid amide derivative represented by the following formula (9): wherein R⁴ represents a straight-chain or branched alkyl group having 7 to 21 carbon atoms, and R⁵ and R⁴ are the same or different from each other and each represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a group represented by the formula -(C₂H₄O)kH (wherein k is a number of 2 to 4). 21. A cleaning composition comprising a glycine derivative represented by the following formula (2): wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms. a hydrogen atom, an alkali metal atom, 1/2(alkaline earth metal atom), an ammonium group, a monoalkanolammonium group with 1 to 22 carbon atoms, a dialkanolammonium group with a total of 2 to 22 carbon atoms, a trialkanolammonium group with a total of 3 to 22 carbon atoms or a protonated basic amino acid. 22. A method for washing skin or hair, which comprises bringing the skin or hair into contact with a composition comprising a glycine derivative represented by the following formula (1): wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ and M₂ are the same or different from each other and each independently represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a trialkanolammonium group having a total of 3 to 22 carbon atoms or a protonated basic amino acid. 23. Use of a cleansing composition comprising a glycine derivative represented by the following formula (1) for washing skin or hair: wherein R represents a straight-chain or branched alkyl group having 11 to 13 carbon atoms, a straight-chain or branched alkenyl group having 11 to 13 carbon atoms or a straight-chain or branched hydroxyalkyl group having 11 to 13 carbon atoms, and M₁ and M₂ are the same or different from each other and each independently represents a hydrogen atom, an alkali metal atom, 1/2 (alkaline earth metal atom), an ammonium group, a monoalkanolammonium group having 1 to 22 carbon atoms, a dialkanolammonium group having a total of 2 to 22 carbon atoms, a trialkanolammonium group having a total of 3 to 22 carbon atoms or a protonated basic amino acid.